Dimethylformamide → Methyl 3-chloro-4-formyl-1H-pyrrole-2-carboxylate

HRID 1874959ノート

反応式

HRID 1874959 の反応式
CN([CH:4]=[O:5])C.O=P(Cl)(Cl)Cl.[Cl:11][C:12]1[CH:16]=[CH:15][NH:14][C:13]=1[C:17]([O:19][CH3:20])=[O:18]>ClC(Cl)C>[Cl:11][C:12]1[CH:16]=[C:15]([CH:4]=[O:5])[NH:14][C:13]=1[C:17]([O:19][CH3:20])=[O:18].[Cl:11][C:12]1[C:16]([CH:4]=[O:5])=[CH:15][NH:14][C:13]=1[C:17]([O:19][CH3:20])=[O:18]

参加物

6

反応物 3

HCID 6228Dimethylformamide2 回HCID 24813Phosphorus oxychlorideHCID 5324605Methyl 3-chloro-1H-pyrrole-2-carboxylate

生成物 2

HCID 86644899Methyl 3-chloro-4-formyl-1H-pyrrole-2-carboxylate収率 27%HCID 86644900methyl 3-chloro-5-formyl-1H-pyrrole-2-carboxylate収率 27%

試薬・触媒・溶媒 1

HCID 63651,1-Dichloroethane溶媒2 回

反応条件

温度
0 °C

実験手順

DMF (0.579 mL, 1.48 mmol) was cooled to 0° C. under nitrogen. POCl3 (0.647 mL, 6.93 mmol) was added to the cold DMF and stirred at 0° C., and a solid formed. Dichloroethane (2 mL) was added to the solid followed by the addition of methyl 3-chloro-1H-pyrrole-2-carboxylate (1.00 g, 6.26 mmol) in dichloroethane (2 mL). The reaction mixture was stirred for 10 minutes at 0° C. and heated to reflux until the starting material was no longer evident by TLC. The reaction mixture was cooled and partitioned between EtOAc and water. The organic layer was separated, washed with saturated NaHCO3, dried over MgSO4, filtered and the EtOAc evaporated. Purification was accomplished by silica gel column chromatography (0-30% EtOAc/hexanes) to afford the title compound (0.320 g, 27%), and methyl 3-chloro-4-formyl-1H-pyrrole-2-carboxylate (0.319 g, 27%). 1H NMR (400 MHz, Acetone-d6) δ ppm 11.95 (br. s., 1H), 9.72 (s, 1H), 7.02 (s, 1H), 3.87 (s, 3H). LCMS: m/z 188.1 (M+1).

後処理

  1. customa solid formed
  2. stirringThe reaction mixture was stirred for 10 minutes at 0° C.
  3. temperatureheated
  4. temperatureto reflux until the starting material
  5. temperatureThe reaction mixture was cooled
  6. custompartitioned between EtOAc and water
  7. customThe organic layer was separated
  8. washwashed with saturated NaHCO3
  9. dry with materialdried over MgSO4
  10. filtrationfiltered
  11. customthe EtOAc evaporated
  12. customPurification

出典と根拠

ORDレコード
ord-e7baa7f5cf1843f8a05231960872650e
出典データセット
uspto-grants-2012_11
特許番号
US08304419B2

反応ノート

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